# US 12,119,444 B2 · Annealed garnet electrolyte separators

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,119,444 B2
- Document ID: US12119444B2
- Status: Granted
- Kind: B2
- Application number: 18/153,305
- Filed: 2023-01-11
- Published: 2023-07-20
- Granted: 2024-10-15
- Earliest claimed: 2016-01-27
- Assignees: QuantumScape Battery, Inc.
- Applicants: Quantumscape Battery, Inc.
- Inventors: Arnold Allenic; Cheng-Chieh Chao; Lei Cheng; Niall Donnelly; William H. Gardner; Timothy Holme; Sriram Iyer; Shuang Li
- Web page: https://patentgrep.com/patent/US12119444B2

## CPC

- H01M 10/0562: Solid materials
- C04B 35/4885: {with aluminium oxide}
- C04B 35/62218: {obtaining ceramic films, e.g. by using temporary supports}
- H01M 10/052: Li-accumulators
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 10/058: Construction or manufacture
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/409: Separators, membranes or diaphragms characterised by the material
- C04B 2235/3203: Lithium oxide or oxide-forming salts thereof
- C04B 2235/3227: Lanthanum oxide or oxide-forming salts thereof
- C04B 2235/6025: Tape casting, e.g. with a doctor blade
- C04B 2235/6567: Treatment time
- C04B 2235/764: Garnet structure A3B2(CO4)3
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Set forth herein are pellets, thin films, and monoliths of lithium-stuffed garnet electrolytes having engineered surfaces. These engineered surfaces have a list of advantageous properties including, but not limited to, low surface area resistance, high Li+ ion conductivity, low tendency for lithium dendrites to form within or thereupon when the electrolytes are used in an electrochemical cell. Other advantages include voltage stability and long cycle life when used in electrochemical cells as a separator or a membrane between the positive and negative electrodes. Also set forth herein are methods of making these electrolytes including, but not limited to, methods of annealing these electrolytes under controlled atmosphere conditions. Set forth herein, additionally, are methods of using these electrolytes in electrochemical cells and devices. The instant disclosure further includes electrochemical cells which incorporate the lithium-stuffed garnet electrolytes set forth herein.

## Claims

### Claim 1

An electrolyte separator,
wherein the electrolyte separator is bound to a substrate selected from a polymer, a glass, or a metal;
wherein the electrolyte separator comprises a bulk, wherein the bulk has a thickness from about 10 nm to about 100 μm;
wherein the bulk is characterized by the chemical formula LiALaBM′cM″DZrEOF,
wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2; 0≤E<2, 10<F<13, M′ is Al, and M″ is selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta; and
wherein either a top or bottom surface of the electrolyte separator is characterized as having a less than 1 μm layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, a hydrate thereof, an oxide thereof, or a combination thereof.

### Claim 2 (depends on 1)

The electrolyte separator of claim 1, wherein the substrate is a metal.

### Claim 3 (depends on 2)

The electrolyte separator of claim 2, wherein the metal comprises nickel (Ni), copper (Cu), steel, stainless steel, combinations thereof, or alloys thereof.

### Claim 4 (depends on 3)

The electrolyte separator of claim 3, wherein the metal comprises nickel (Ni).

### Claim 5 (depends on 3)

The electrolyte separator of claim 3, wherein the metal comprises copper (Cu).

### Claim 6 (depends on 3)

The electrolyte separator of claim 3, wherein the metal comprises steel or stainless steel.

### Claim 7 (depends on 1)

The electrolyte separator of claim 1, wherein either the top or bottom surface of the electrolyte separator is characterized as having substantially no layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof, as characterized by Raman spectroscopy.

### Claim 8 (depends on 1)

The electrolyte separator of claim 1, wherein either the top or bottom surface of the electrolyte separator is characterized as having substantially no layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof, as characterized by FT-IR.

### Claim 9 (depends on 1)

The electrolyte separator of claim 1, wherein either the top or bottom surface of the electrolyte separator is characterized as having substantially no layer thereupon comprising lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof, as characterized by XPS.

### Claim 10 (depends on 1)

The electrolyte separator of claim 1, having a Li-metal interface area specific resistance between 0 and 15 Ωcm2 at 60° C.

### Claim 11 (depends on 10)

The electrolyte separator of claim 10, having a Li-metal interface area specific resistance less than 2 Ωcm2 at 60° C.

### Claim 12 (depends on 1)

The electrolyte separator of claim 1, having a Li-metal interface area specific resistance less than 2 Ωcm2 at 25° C.

### Claim 13 (depends on 1)

The electrolyte separator of claim 1, having a Li-metal interface area specific resistance less than 20 Ωcm2 at −25° C.

### Claim 14 (depends on 1)

The electrolyte separator of claim 1, having a top or bottom surface that has a carbon concentration at the surface of less than 5 atomic %.

### Claim 15 (depends on 1)

The electrolyte separator of claim 1, having a top or bottom surface that has a hydrogen concentration at the surface of less than 5 atomic %.

### Claim 16 (depends on 1)

An electrochemical cell comprising the electrolyte separator of claim 1.

### Claim 17 (depends on 16)

The electrochemical cell of claim 16 further comprising a lithium metal anode.

### Claim 18 (depends on 16)

The electrochemical cell of claim 16, further comprising an electrolyte wherein the electrolyte comprises a lithium salt.

### Claim 19 (depends on 18)

The electrochemical cell of claim 18, wherein the lithium salt is LiFTSi or LiPF6.

### Claim 20 (depends on 19)

The electrochemical cell of claim 19, wherein the electrolyte further comprises a solvent selected from ethylene carbonate, dimethyl carbonate, and a combination thereof.

### Claim 21 (depends on 1)

A method of cycling lithium through an electrolyte separator, comprising
providing an electrolyte separator according to claim 1;
and cycling at least 10 μm of lithium metal at a current of at least 1 mA/cm2 or greater.

### Claim 22 (depends on 21)

The method of claim 21, comprising cycling at least 20 μm of lithium metal at a current of at least 2 mA/cm2 or greater.